EP3041872A1 - Biobasierte polycarboxylatether und verfahren zu ihrer herstellung - Google Patents
Biobasierte polycarboxylatether und verfahren zu ihrer herstellungInfo
- Publication number
- EP3041872A1 EP3041872A1 EP14759135.8A EP14759135A EP3041872A1 EP 3041872 A1 EP3041872 A1 EP 3041872A1 EP 14759135 A EP14759135 A EP 14759135A EP 3041872 A1 EP3041872 A1 EP 3041872A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- bio
- salt
- independently
- polycarboxylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
- C08F216/1425—Monomers containing side chains of polyether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
- C08F216/1425—Monomers containing side chains of polyether groups
- C08F216/1433—Monomers containing side chains of polyethylene oxide groups
Definitions
- the invention relates to processes for the preparation of polycarboxylate ethers in which at least one bio-based starting material is used, as well as polycarboxylate ethers which are at least partially biobased.
- Bio-based materials and products are at least partially made from biological materials, especially from renewable resources. They have a favorable carbon footprint because they are not or only partially based on fossil fuels. In addition, they can be produced sustainably and increasingly cheaply if the underlying biological material is readily available, especially if by-products or residues from agriculture and forestry are used.
- Polycarboxylate ethers are produced in the prior art by polymerization reactions or polymer-analogous reactions, using as starting materials conventional petroleum-based precursors.
- bio-based polycarboxylate ethers which are based at least partly on biological materials and in particular renewable raw materials, are not yet known.
- EP 2 255 680 A1 describes polymers of maleic acid, allyl ether and (meth) acrylic acid, which are in particular polycarboxylate ethers, and their preparation and uses.
- EP 1 348 729 A1 describes typical polycarboxylate ethers with polyether side chains and their use in the construction sector, in particular as dispersants and condenser in cements.
- WO2005 / 090416 A1 describes polycarboxylate ethers which have, inter alia, amide-group-linked side chains and their uses in the construction sector in hydraulically setting compositions.
- EP 2 161 247 A1 describes uses of polycarboxylic ethers in cement compositions wherein the polymers are used as mixtures with antioxidants and other additives.
- the object of the present invention is to provide novel processes and products which overcome the abovementioned disadvantages.
- the object of the present invention is to provide novel bio-based products and processes for their preparation.
- the products are intended to be used in particular in the construction sector and allow significant CO 2 savings because of their distribution.
- the sustainability and CO 2 balance of cement, gypsum, lime and other hydraulically setting compositions are to be improved, which are implemented in large quantities.
- the object of the invention is in particular to provide bio-based polycarboxylate ethers.
- the bio-based polycarboxylate ethers should be as simple and accessible in large quantities. They should be bio-based to the highest possible proportion. As far as possible, they should not differ in their properties or only slightly from conventional polycarboxylate ethers. In particular, their effectiveness against analogous products from fossil fuels should not be reduced.
- the object underlying the invention is achieved by methods, polycarboxylate ethers, uses, hydraulically settable compositions and moldings according to the claims.
- the invention relates to a process for the preparation of polycarboxylate ethers in which at least one bio-based starting material is used. Therefore, the polycarboxylate ether prepared is biobased.
- Polycarboxylate ethers are comb polymers having a backbone having carboxy groups and side chains having polyether groups, especially those based on polyethylene oxide (polyethylene glycol; PEG) and / or polypropylene oxide.
- the side chains may have further functional groups, in particular ester and amide groups. Ester groups serve, in addition to ether and amide groups, in particular for linking the main chain with side chains.
- Polycarboxylate ethers with ester groups are therefore also referred to in the art as "polycarboxylate esters”.
- starting material means that the material is chemically converted to the polycarboxylate ether during processing, ie it is consumed.
- the polycarboxylate ether can be completely or partially bio-based. This depends on the extent to which bio-based starting materials are used in the production.
- bio-based means according to the invention that a compound, a material or the like, for example a starting material or a polycarboxylate ether, has been prepared at least in part from biological materials, from renewable agricultural materials or forestry materials
- the materials are in particular of plant or animal origin
- bio-based starting materials are based in particular on renewable raw materials, above all on agricultural or forestry production.
- the bio-based starting materials can be obtained directly from such materials, or be prepared by subsequent reactions of such materials.
- the subsequent reactions can be biochemical Be or include processes such as fermentation processes, or other processes such as organic syntheses and reactions.
- the polycarboxylate ethers according to the invention are therefore based at most partially, and in a particularly preferred embodiment not at all, on fossil raw materials, in particular not on crude oil. Products based only on fossil raw materials are not referred to as bio-based according to the invention and in accordance with common usage.
- Fossil resources originated from dead organisms in geological past and include lignite, hard coal, peat, natural gas and petroleum.
- at least one biobased starting material is selected from the group consisting of polyethylene oxide, terminally modified polyethylene oxide, acrylic acid or a salt thereof, methacrylic acid or a salt thereof and / or maleic acid or a salt thereof.
- the term "acid" in the context of this application in organic acids not only the protonated acid, but also salts of the acid and partially neutralized mixtures thereof.
- polyethylene oxide is used as the bio-based starting material.
- the polyethylene oxide may be terminally modified on one side of the polyethylene oxide chain or on both sides.
- the term "side" refers to the two chain ends of the polymer
- the polyethylene oxide is terminally modified on one side only and has a free hydroxy group on the other side.
- the terminally modified polyethylene oxide is at one end
- the alkenyl radical preferably has a single C-C double bond
- the alkenyl radical preferably has from 2 to 10, in particular from 2 to 6, carbon atoms
- the alkenyl radical is preferably selected from allyl, vinyl, methallyl and isoprenyl the chain can be unsubstituted and thus have a free OH group, or be substituted, in particular by a Alkyl group.
- unsaturated derivatives of polyalkylene oxide can be incorporated in a simple way by polymerization in polycarboxylate.
- the biobased modified polyalkylene oxide derivative is preferably a compound of the formula (Ia): R 1 -O- [AO] n -R 2 (Ia)
- R 1 is an alkenyl group
- R 2 is H, an alkyl group having 1 to 20 C atoms, or an aryl,
- a independently of one another represents a C 2 - to C 6 -alkylene group
- n 2 to 300, in particular 3 to 200 or 5 to 150, is.
- R 2 H.
- Such derivatives of polyalkylene oxides are generally particularly well available.
- the monomer of the formula R 1 -O- [AO] n -H is, in particularly preferred embodiments, isoprenylpolyethylene glycol, allylpolyethyleneglycol, methallylpolyethyleneglycol, isobutenylpolyethyleneglycol or
- the radical R 2 is different from H, and in particular a Ci to C 6 alkyl group.
- the monomer may then be, for example, (isoprenyl polyethylene glycol) methyl ether, (allyl polyethylene glycol) methyl ether, (vinylpolyethylene glycol) methyl ether, (isoprenyl polyethylene glycol) ethyl ether, (allyl polyethylene glycol) ethyl ether, (methallyl polyethylene glycol) ethyl ether or (vinyl polyethylene glycol) ethyl ether.
- the biobased terminally modified polyalkylene oxide is terminally modified only on one side of the chain, the attached radical being non-reactive and in particular having no CC double bond.
- the radical is preferably an alkyl group, in particular methyl or ethyl.
- Such derivatives of polyalkylene oxide can be easily prepared by polymer-analogous reactions, in particular esterification or etherification, incorporated into polycarboxylate ethers. In this case, preference is given to a bio-based monomer of the formula (IIa)
- R 2 is an alkyl group having 1 to 20 C atoms, or an aryl
- a independently of one another represents a C 2 - to C 6 -alkylene group
- n 2 to 300, in particular 3 to 200 or 5 to 150.
- At least one bio-based starting material which is a biobased organic compound having 2 or 3 carbon atoms or obtained from a biobased organic compound having 2 or 3 carbon atoms is used in the process according to the invention.
- the bio-based organic compound having 2 or 3 carbon atoms preferably consists exclusively of C, H and O and optionally has one or two double bonds.
- the biobased organic compound having 2 or 3 carbon atoms is purified before it is further reacted to the polycarboxylate ethers or to bio-based source materials for their preparation.
- bio-based source materials for their preparation.
- intermediates from renewable raw materials are often not available in consistent quality. This is problematic or even dangerous when incorporated into cements, lime or gypsum if the products do not have the desired stability and damage such as cracks or blisters occurs over long periods of time.
- biobased low molecular weight compounds, in particular organic compounds having 2 or 3 carbon atoms are used as starting materials, they can be purified to polycarboxylate ethers before further processing. As low molecular weight bio-based compounds in high Purity are accessible, a high and continuous quality of derived bio-based products can be achieved.
- the biobased organic compounds having 2 or 3 carbon atoms are ethanol, glycerol, ethylene, acrolein, 3-hydroxypropionic acid, 2-hydroxypropionic acid and / or salts thereof.
- the polyethylene oxide was obtained from bio-based ethanol ("bioethanol”)
- bioethanol bio-based ethanol
- the polyethylene oxide was obtained by a process comprising the steps of (a) dehydrating bio-based ethanol to ethylene,
- Bioethanol can be obtained by fermentation from biological raw materials, in particular from sugars or sugar-containing materials.
- Sugars are generally biobased and can be isolated from a variety of renewable resources.
- Particularly suitable raw materials are plants with high sugar content, such as sugar cane or sugar beets. From such plants, first, a high-sugar extract such as molasses can be separated. The sugar content can optionally be increased by further purification steps, such as distillation. The extract may then be fermented using suitable yeasts, bacteria and / or enzymes to yield ethanol.
- suitable yeasts, bacteria and / or enzymes to yield ethanol.
- the ethanol can be dehydrated to give ethylene.
- the ethylene can then be converted to ethylene oxide. This reaction is usually carried out with oxygen in the presence of catalysts.
- the bio-based polyethylene oxide is then prepared by polymerization of ethylene oxide.
- the polyethylene oxide can be modified with a desired terminal group, for example an alkenyl group and / or an alkyl group.
- Bio-based polyethylene oxides, optionally terminally modified are commercially available from India Glycol, IN, for example under the trade designations lgsurf-1200 AP (vinyl-terminated) or Polymeg 1000 M (methyl-terminated).
- the acrylic acid or a salt thereof was obtained from sugars.
- the acrylic acid or a salt thereof has been obtained by a method with the steps
- the starting material used in this process in step (a) is preferably glycerol or a sugar, in particular glucose, or a plant extract with a high sugar content.
- the sugar is then reacted to 2-hydroxypropionic acid (lactic acid) and / or 3-hydroxypropionic acid (3-HPA) and / or salts thereof, preferably by fermentation using suitable yeasts, bacteria and / or enzymes.
- 2-hydroxypropionic acid lactic acid
- 3-hydroxypropionic acid 3-hydroxypropionic acid
- the bio-based acrylic acid or a salt thereof may be subsequently obtained by dehydrating the hydroxypropionic acid.
- Such a method is known in the art and is described in DE 10 2006 039 203 A1.
- the acrylic acid or a salt thereof has been obtained by a process comprising the steps of (a) dehydrating biobased glycerol to acrolein, and
- Glycerol is a by-product of biodiesel production. This is usually done by transesterification of mostly vegetable oils with methanol. In this case, a triacylglyceride is reacted with methanol to glycerol and fatty acid methyl esters. Also, a biotechnological production by fermentation with yeast is known. By dehydration, the glycerol can become acrolein followed by oxidation to bio-based acrylic acid or a salt thereof. Such a method is known in the art and is described in WO2006 / 092272 or the corresponding US2009 / 0134357 A1. Methods of producing bio-based maleic acid have been described in the prior art. For example, Novozymes, DK, has developed a process to produce biobased maleic acid by microorganisms.
- biobased acrylic acid or a salt thereof and biobased polycarboxylate ethers are used to prepare the polycarboxylate ethers.
- the bio-based polycarboxylate ethers may be terminally modified. Such a combination makes it possible to achieve a relatively high bio-based content.
- bio-based methacrylic acid Preferably, methacrylic acid or a salt thereof is used which has been prepared from 2-hydroxyisobutyric acid or terf-butanol. Both starting materials are accessible in large quantities from bio-based raw materials. Corresponding methods are described, for example, in Rohwerder and Müller, Microbial Cell Factories 2010, 9, 13, pp. 1-10.
- biobased acrylic acid and / or bio-based methacrylic acid or salts thereof and biobased polycarboxylate ethers are used to prepare the polycarboxylate ethers.
- the invention also provides a polycarboxylate ether which is at least partially bio-based.
- the polycarboxylate ether is obtainable in particular according to the process of the invention.
- the polycarboxylate according to the invention has 14 carbon atoms. By determining the 14 C content, it can be clearly determined whether and to what proportion a polycarboxylate ether is bio-based. Bio-based polycarboxylate ethers differ from non-bio-based polycarboxylate ethers in a measurable proportion of the carbon isotope 14 C.
- the isotope 14 C in the atmosphere has a half-life of approximately 5730 years and is incorporated into living biological organisms.
- a fresh organic sample contains about 1 ppt (parts per trillion, 10 "12 ) 14 C atoms, based on the sum of all C atoms.
- the amount of bound radioactive 14 C atoms decreases according to the law of decomposition, measurable but only over long periods of time
- Organic compounds made from fossil fuels are not "bio-based” and have no measurable 14 C content.
- the 14 C content of a sample can be determined analytically. From the content it can be determined to what extent the polycarboxylate ether is biobased.
- the 14 C portion and the bio-based portion of the polycarboxylate ethers are determined according to ASTM D6866 "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis".
- the proportion of 14 C atoms in the polycarboxylate ether is preferably more than 0.1 ppt, in particular more than 0.25 ppt, more than 0.5 ppt or more than 0.8 ppt, based on the sum of all C atoms present.
- the polycarboxylate ether is at least 10%, more preferably greater than 25%, greater than 50%, greater than 75%, greater than 90%, greater than 95%, greater than 98%, or 100% % bio-based.
- the polycarboxylate ether has side chains attached via ester, ether, amide and / or imide groups to a backbone. Preference is given to ester, ether and / or amide groups, in particular esters and / or ether groups.
- the main chain has at least one acid unit or a salt thereof.
- the acid moiety is in particular an ⁇ -unsaturated mono- or dicarboxylic acid, such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid, crotonic acid or fumaric acid.
- the acid moiety is preferably acrylic acid, methacrylic acid, maleic acid and / or a salt thereof and / or combinations thereof.
- the side chains contain polyalkylene oxide side chains, preferably polyethylene oxide units.
- at least 50 mol%, in particular at least 75 mol%, preferably at least 95 mol% or 100 mol% of the side chains comprise or consist of polyalkylene oxide.
- a proportion of ethylene oxide units in the polyalkylene oxide side chains, based on all the alkylene oxide units present in the side chains, is preferably more than 90 mol%, in particular more than 95 mol%, preferably more than 98 mol%, in particular 100 mol%
- the polyalkylene oxide side chains preferably have no hydrophobic groups, in particular no alkylene oxides having three or more carbon atoms.
- a high proportion of ethylene oxide units or a low content of alkylene oxides having three or more carbon atoms reduces the risk of undesirable air entry.
- the polyalkylene oxide side chains have in particular a structure according to formula - [AO] n -R a .
- A C 2 - to C 5 -alkylene, which may be branched or unbranched.
- R a is preferably H, a C 2 to C 20 alkyl group, cyclohexyl group or alkylaryl group.
- n 2 to 300, in particular 3 to 200 or 5 to 150.
- a weight-average molecular weight (M w ) of the polycarboxylate is in particular 5 ⁇ 00 - 150 ⁇ 00 g / mol, preferably 10 ⁇ 00 - 100 ⁇ 00 g / mol.
- a number-average molecular weight (M n ) of the polycarboxylate ether is advantageously 3000-10000 g / mol, in particular 8-100-7000 g / mol.
- the polycarboxylate ether preferably comprises or consists of the following partial structural units: a) a molar proportions of a partial structural unit S1 of the formula (I)
- R 1 each independently, is -COOM, -SO 2 -OM,
- R 2 , R 3 , R 5 , R 6 , R 9 , R 10 , R 13 and R 14 are each independently, H or an alkyl group having 1 to 5 carbon atoms,
- R 4 , R 7 , R 11 and R 15 each independently represent H, -COOM or an alkyl group of 1 to 5 carbon atoms; M, independently of one another, is H + , an alkali metal ion
- R 16 independently of one another, stand for NH 2 , -NR b R c , -OR d NR e R f
- R b and R c independently of each other, represent a C 1 to C 20 alkyl group, cycloalkyl group
- Alkylaryh group or aryl group or for a hydroxyalkyl group or for an acetoxyethyl- (CH 3 -CO-O-CH 2 -CH 2 -) or a hydroxyisopropyl- (HO-CH (CH 3 ) -CH 2 -) or one
- Acetoxyisopropyl group (CH 3 -CO-O-CH (CH 3 ) -CH 2 -); or R b and R c together form a ring, of which the
- Nitrogen is a part of a morpholine or
- R d is a C 2 -C 4 -alkylene group
- R e and R f are each independently a C 1 to C 20 alkyl group, cycloalkyl group, alkylaryl group,
- the sequence of the partial structural units S1, S2, S3 and S4 can be alternating, block-like or random. Furthermore, it is also possible that, in addition to the partial structural units S1, S2, S3 and S4, further partial structural units are present.
- the partial structural units S1, S2, S3 and S4 together have a weight fraction of at least 50% by weight, in particular at least 90% by weight, very particularly preferably at least 95% by weight, of the total weight of the polycarboxylate ether.
- a ratio of a / (b + c + d) is in particular in the range of 1-5.
- the polycarboxylate can be prepared based on acrylic or methacrylic acid monomers, which is interesting from an economic point
- polycarboxylate ethers in the present context results in a good reduction in viscosity.
- Such polycarboxylate ethers can be prepared on the basis of maleic acid monomers.
- Such polycarboxylate ethers can be prepared, for example, starting from (meth) acrylic acid esters, vinyl (meth) allyl or isoprenol ethers.
- R 2 and R 5 are mixtures of H and -CH 3 . Preference is given to mixtures with 40-60 mol% H and 40-60 mol% CH 3 . If the corresponding partial structural units are present, this also applies in particular to R 9 and R 13 . In this case, moreover, R 3 and R 6 are preferably H, and, if the corresponding partial structural units are present, R 9 and R 13 are H.
- R 1 COOM
- R 2 H
- R 5 - CH 3
- R 1 COOM
- R 1 is COOM
- R 2 and R 5 independently of one another, are H, -CH 3 or mixtures thereof.
- R 2 and R 5 are very particularly advantageous for mixtures of H and -CH 3 .
- Preference is given to mixtures with 40-60 mol% H and 40-60 mol% CH 3 .
- R 9 and R 13 this also applies in particular to R 9 and R 13 ;
- R 3 and R 6 are H.
- R 4 and R 7 independently of one another, are H or -COOM, preferably H.
- the polycarboxylate ethers according to the invention can be prepared in a manner known per se.
- the polymer-analogous reaction or the radical polymerization are used.
- the polycarboxylate ethers can be prepared after the polymer-analogous reaction. First, a main chain is produced, which is then equipped with side chains. Polymer-analogous reactions are known per se and are described, for example, in WO97 / 35814A1, WO95 / 09821A2, DE 100 15 135A1, EP 1 138697A1, EP1348729A1 and WO2005 / 090416A1. Details of the polymer-analogous reaction are disclosed, for example, in EP 1 138 697 B1 on page 7 line 20 to page 8 line 50, and in the examples contained therein, or in EP 1 061 089 B1 on page 4, line 54 to page 5 line 38 and in the examples.
- the polymer-analogous process comprises in particular the steps: a) Provision and / or preparation of a base polymer BP comprising or consisting of a structural unit of the formula V
- the base polymer BP in step a) is in particular a polyacrylic acid, a polymethacrylic acid and / or a copolymer of acrylic acid and methacrylic acid.
- a number-average molecular weight (M n ) of the base polymer BP of the formula (V) is in particular equal to 500 - 20 ⁇ 00 g / mol, in particular 500 - 10 ⁇ 00 g / mol, more preferably 3 ⁇ 00 - 6 ⁇ 00 g / mol.
- Such base polymers BP can be prepared in a conventional manner from acrylic acid monomers and / or methacrylic acid monomers. However, it is also possible, for example, to use maleic acid monomers and / or maleic anhydride monomers. This can be advantageous, inter alia, for economic and safety aspects.
- the base polymer BP is prepared in step a) in particular by aqueous free-radical polymerization, for example of acrylic acid and / or methacrylic acid, in the presence of a free-radical initiator and / or a molecular weight regulator.
- aqueous free-radical polymerization for example of acrylic acid and / or methacrylic acid
- the radical initiator in step a) comprises in particular Na, K or ammonium peroxodisulfate. Also suitable as a radical initiator in step a) is, for example, a redox couple based on H 2 O 2 / Fe 2+ .
- the molecular weight regulator in step a) is preferably an alkali metal sulfite or hydrogen sulfite. Also advantageous is a Phosphinklarederivat.
- the molecular weight regulator in step a) may also be an organic compound containing a thiol group.
- Corresponding base polymers BP can in principle also be obtained commercially from various suppliers.
- the esterification in step b among other acids and / or bases, for example as catalysts, can be added.
- the esterification takes place at elevated temperatures of 120-200 ° C., in particular 160-180 ° C. This can significantly improve the yield.
- step b) The compounds of the formulas V, VI and VII used in step b) are commercially available from various suppliers.
- the polycarboxylate ethers may also be prepared by a free radical polymerization reaction wherein the copolymer is obtained from corresponding ethylenically unsaturated acid, ester and amide monomers in the presence of a free radical generator.
- This process also referred to below as “copolymerization process”, comprises in particular a copolymerization of:
- a, b, c and d represent the mole fractions of the respective monomers M1, M2, M3 and M4, where a, b, cd, M, R 1 - R 16 , m and p are as defined above, wherein R 8 is preferably H is.
- the monomers M2, M3 and M4 can be prepared in a manner known per se by esterification or amidation of acrylic acid, methacrylic acid, maleic acid and / or maleic anhydride with compounds of the formulas VI, VII or VIII (see above).
- the invention also provides a hydraulically settable composition comprising a polycarboxylate ether according to the invention and a hydraulically settable binder.
- a hydraulically settable composition is meant compositions containing hydraulically settable binders such as inorganic materials which cure in the presence of water, suitable binders and compositions are known to those skilled in the field of construction chemistry
- the hydraulically settable binder in the composition is or comprises cement, gypsum or lime.Custom cements are, for example, Portland cements or high-alumina cements and their respective mixtures with customary additives.
- the polycarboxylate ether according to the invention is preferably used in an amount of from 0.01 to 5% by weight, in particular from 0.05 to 2% by weight or from 0.1 to 1% by weight, based on the weight of the hydraulically settable binder ,
- the polycarboxylate ether is preferably used in the form of a liquid composition, in particular as an aqueous solution.
- the polycarboxylate ether according to the invention is preferably used as a dispersant and in particular as a plasticizer, as a water reducer, to improve the processability and / or to improve the flowability of the hydraulically settable compositions prepared therewith, and to improve the stability of the cured products.
- hydraulically settable compositions having extended processability can be obtained according to the invention. This means that the composition can still be processed for a relatively long time after the addition of water and the polycarboxylate ether, in comparison to compositions which do not contain the polycarboxylate ether.
- the flowability of a hydraulically settable composition is increased by the polycarboxylate ether.
- the slump is preferably at least 5%, in particular more than 10%, even more preferably more than 15%, or increased more than 25%, each compared to an identical composition without polycarboxylate ether.
- the slump is determined, for example, with a flowable sample with 0.2 wt .-% polycarboxylate (based on the amount of hydraulically setting binder), in particular after mixing with water and 30 seconds of intensive stirring in a miniconus of 50 mm, filling height 51 mm , after 75 seconds.
- the slump can be determined as described in the embodiments. Standard conditions according to DIN EN 132790-2 or DIN EN 12350-5 - Testing fresh concrete - Part 5: Slump dimension can also be used.
- the polycarboxylate ether according to the invention can be used as a dispersant or as a constituent of a dispersant in conjunction with other components.
- Further constituents may be other plasticizers, for example polycarboxylate ethers (PCE), lignosulfonates, sulfonated naphthalene-formaldehyde condensates or sulfonated melamine-formaldehyde condensates; or accelerators, retarders, shrinkage reducers, defoamers, air entrainers or foaming agents.
- PCE polycarboxylate ethers
- lignosulfonates lignosulfonates
- sulfonated naphthalene-formaldehyde condensates or sulfonated melamine-formaldehyde condensates
- accelerators, retarders, shrinkage reducers, defoamers, air entrainers or foaming agents Typically, the proportion
- the polycarboxylate ether according to the invention can also be used in solid state, for example as flakes, powders, flakes, pellets, granules or plates. Such solid additives are easy to transport and store.
- the polycarboxylate ether in the solid state may be a constituent of a so-called dry mix, for example a cement composition, which is shelf stable for a long time and is typically packaged in bags or stored in silos and used. Such a dry mixture can be used even after a long storage time and has a good flowability.
- the polycarboxylate ether of the invention can be added to a hydraulically settable composition with, or shortly before, or shortly after the addition of the water.
- Particularly suitable here is the addition in the form of an aqueous solution or dispersion, in particular as Mixing water or as part of the mixing water, exposed.
- the preparation of the aqueous solution is carried out in particular by subsequent mixing with water.
- the polycarboxylate ether according to the invention can also be added to a hydraulically settable composition before or during its grinding operation, for example the cement-cement-cement grinding process.
- the invention also provides moldings obtainable by setting and curing a hydraulically settable composition according to the invention.
- the term "shaped body" refers to any three-dimensional solid body which has received a shape, such as movable construction elements, buildings and building parts, floors and coatings.
- the invention also provides the use of a polycarboxylate ether according to the invention as a dispersant, in particular as a plasticizer, for hydraulically settable compositions.
- the processes according to the invention polycarboxylate ethers and uses solve the problem on which the invention is based.
- the invention provides bio-based polycarboxylate ethers and simple and efficient processes for their preparation. Depending on whether only a part or all starting materials are biobased, a desired bio-based content can be adjusted. When bio-based acid moieties and bio-based polyalkylene oxide side chains are used, a bio-based content of up to 100% can be achieved.
- bio-based polycarboxylate ethers are provided which have an advantageous CO 2 balance. They allow the construction industry considerable CO 2 savings. They can be used environmentally friendly for sustainable applications and reduce the cost of carbon credits.
- the 14 C content allows proof of the bio-based origin and the proportion.
- the process according to the invention also makes it possible to prepare polycarboxylate ethers from bio-based raw materials which have a high and consistent quality.
- the high and continuous quality can be achieved according to the invention because synthetic routes are followed using low molecular weight biobased intermediates.
- low molecular weight intermediates such as ethanol, glycerol, acrolein or 2- or 3-hydroxypropionic acid, quality fluctuations of the final product can be prevented.
- the bio-based polycarboxylate ethers are therefore also suitable for applications where no quality fluctuations may occur, as with dispersants for cement compositions.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
Claims
Priority Applications (1)
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EP14759135.8A EP3041872A1 (de) | 2013-09-06 | 2014-09-01 | Biobasierte polycarboxylatether und verfahren zu ihrer herstellung |
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EP13183378 | 2013-09-06 | ||
EP14759135.8A EP3041872A1 (de) | 2013-09-06 | 2014-09-01 | Biobasierte polycarboxylatether und verfahren zu ihrer herstellung |
PCT/EP2014/068474 WO2015032710A1 (de) | 2013-09-06 | 2014-09-01 | Biobasierte polycarboxylatether und verfahren zu ihrer herstellung |
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US (1) | US20160194430A1 (de) |
EP (1) | EP3041872A1 (de) |
WO (1) | WO2015032710A1 (de) |
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SG101990A1 (en) | 2000-08-11 | 2004-02-27 | Nippon Catalytic Chem Ind | Cement dispersant and cement composition comprising this |
EP1348729A1 (de) * | 2002-03-25 | 2003-10-01 | Sika Schweiz AG | Polymere in festem Aggregatzustand |
EP1577327A1 (de) * | 2004-03-19 | 2005-09-21 | Sika Technology AG | Amid-und Estergruppen aufweisendes Polymer, dessen Herstellung und Verwendung |
CN1984934A (zh) * | 2004-07-12 | 2007-06-20 | 株式会社日本触媒 | 生产水泥分散剂的方法和用于水泥分散剂的聚羧酸类型聚合物 |
TWI438187B (zh) * | 2005-02-28 | 2014-05-21 | Evonik Degussa Gmbh | 丙烯酸和基於可再生原料之吸水聚合物結構及二者之製備方法 |
WO2009155086A2 (en) * | 2008-05-30 | 2009-12-23 | E. I. Du Pont De Nemours And Company | Renewably resourced chemicals and intermediates |
US8519029B2 (en) * | 2008-06-16 | 2013-08-27 | Construction Research & Technology Gmbh | Copolymer admixture system for workability retention of cementitious compositions |
ES2395988T3 (es) * | 2008-09-05 | 2013-02-18 | Sika Technology Ag | Procedimiento para la estabilización de policarboxilatos |
EP2463314A1 (de) * | 2010-12-10 | 2012-06-13 | Sika Technology AG | Herstellung von Kammpolymeren durch Veresterung |
ES2426730T3 (es) * | 2011-05-10 | 2013-10-24 | Sika Technology Ag | Polímero de ácido maleico, éteres alílicos y compuestos de ácido (met)acrílico, su preparación y su utilización |
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2014
- 2014-09-01 EP EP14759135.8A patent/EP3041872A1/de active Pending
- 2014-09-01 WO PCT/EP2014/068474 patent/WO2015032710A1/de active Application Filing
- 2014-09-01 US US14/912,003 patent/US20160194430A1/en not_active Abandoned
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US20160194430A1 (en) | 2016-07-07 |
WO2015032710A1 (de) | 2015-03-12 |
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